EP0946640B1 - Thermoplastic olefin compositions - Google Patents
Thermoplastic olefin compositions Download PDFInfo
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- EP0946640B1 EP0946640B1 EP97952488A EP97952488A EP0946640B1 EP 0946640 B1 EP0946640 B1 EP 0946640B1 EP 97952488 A EP97952488 A EP 97952488A EP 97952488 A EP97952488 A EP 97952488A EP 0946640 B1 EP0946640 B1 EP 0946640B1
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- EP
- European Patent Office
- Prior art keywords
- compatibilizer
- ethylene
- weight percent
- elastomer
- polypropylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
Definitions
- the invention relates to novel Thermoplastic Olefin compositions comprising polypropylene, and ethylene-alpha olefin elastomer and a compatibilizer comprising an ethylene-propylene copolymer having a propylene content of greater than 80 weight percent.
- the ethylene-propylene copolymer compatibilizer imparts a greater degree of compatibility between the polypropylene and elastomer phases yielding improved physical properties.
- TPOs Thermoplastic Olefin Compositions
- TPOs are defined as blends of polypropylene, olefinic elastomers and optionally fillers and other compounding ingredients.
- TPOs are multiphase polymer blends where the polypropylene forms a continuous matrix phase and the elastomer and fillers are the dispersed components.
- the polypropylene matrix imparts tensile strength and chemical resistance to the TPO while the elastomer imparts flexibility and impact resistance.
- EP ethylene-propylene copolymers
- EPDM ethylene-propylene-diene terpolymers
- TPOs The major market for TPOs is in the manufacture of automotive parts, especially bumper fascia. These parts are generally made using injection molding processes. To increase efficiency and reduce costs it is necessary to decrease molding times and reduce wall thickness in the molds. To accomplish these goals, manufacturers have turned to high melt flow polypropylenes (Melt Flow Rate > 35). These high melt flow rate (MFR) resins are difficult to toughen, resulting in products that have low impact strength.
- MFR melt flow polypropylene
- U.S.-A- 5,681,897 discloses the use of substantially linear ethylene-alpha olefin copolymers having a degree of long chain branching as impact modifiers for polypropylene as well as other thermoplastic resins. While the use of these elastomers appears to lead to an improvement in impact strength, there is still a need for impact strength and flexibility in TPOs made with high MFR polypropylene resins.
- WO-A-96/06132 discloses a blend comprising 50-80% of a thermoplastic component and 20-50% of an elastomeric component.
- thermoplastic olefin composition comprising:
- thermoplastic olefin compositions of the present invention are prepared by blending the high melt flow rate (MFR) polypropylene resin with the ethylene-alpha olefin elastomer and the compatibilizer comprising an ethylene-propylene copolymer having a propylene content of 80 to 92 weight percent. It has been found that the high propylene content copolymer acts as a compatibilizer between the polypropylene phase and the elastomeric phase resulting in excellent dispersion of the elastomer throughout the polypropylene matrix.
- MFR melt flow rate
- the polypropylene phase of the TPO comprises of polypropylene homopolymer having a relatively high melt flow rate (MFR). Specifically the MFRs should range from 20 to 100 g/10 min with a MFR of 35 to 70 g/10 min preferred.
- the polypropylene component will comprise 88 to 50 weight percent of the TPO with a polypropylene content of 65 to 75 weight percent preferred and a polypropylene content of 70 weight percent most preferred.
- the elastomer component of the TPO comprises either the ethylene-C 3 to C 20 alpha olefin elastomer copolymer or the ethylene-alpha olefin-diene elastomer (terpolymer) as defined above.
- the elastomer generally will have a number average molecular weight of from 30,000 to 500,000 with a range of 50,000 to 100,000 preferred.
- the ethylene content of the elastomer will generally range from 45 to 80 weight percent with 45 to 65 weight percent preferred.
- the elastomeric component of the TPO comprises at least 10 weight percent with 20 to 40 weight percent preferred.
- the ethylene propylene copolymer compatibilizer will have a number average molecular weight of from 40,000 to 300,000 with 80,000 to 200,000 being preferred.
- the compatibilizers will generally have a molecular weight distribution (MWD) of from 1.8 to 4.5 with from 2 to 3 preferred.
- the propylene content will vary from 80 to 92 weight percent with 83 to 91 weight percent preferred and 85 to 90 weight percent most preferred.
- the preferred copolymers will exhibit a crystallinity of from 2 to 65% of that of isotactic homopolypropylene, preferably 5 to 40%.
- the high propylene copolymer When used as a compatibilizer in TPOs, the high propylene copolymer will be employed in a range of from 2 to 15 weight percent with 3 to 7 weight percent preferred.
- TPOs Other materials typically used in the preparation of TPOs, such as fillers, can also be used in the practice of the invention.
- Figures 1A and 1B are photomicrographs showing the dispersion of elastomer in a 70 MFR polypropylene mixture, without and with the compatibilizer of this invention, respectively.
- Figure 2A and 2B are sets of TEM images of TPO compositions with and without the compatibilizer of the invention, respectively.
- Figures 3A and 3B are schematic diagams of a section of TPO following a notched Izod impact test, without and with the compatibilizer of this invention, respectively.
- Figures 4A to 4D are a series of photomicrographs of TPO compositions exhibiting fracture after impact, comparing compositions with and without the compatibilizer of this invention.
- the major component of the TPOs of the invention comprises polypropylene, preferably, isotactic polypropylene.
- the polypropylene will comprise between 88 and 50 weight percent of the total TPO composition with between 75 and 65 weight percent preferred.
- the polypropylene should have an MFR of at least 20 up to 100, preferably 35 to 75 and more preferably 70.
- the polypropylenes used in the practice of the invention can be prepared using any known technology for the production of polypropylene. This includes the use of traditional Ziegler-Natta catalyst systems as well as new catalyst systems such as metallocene catalyst systems such as those exemplified in WO-A-94/28034. As isotactic polypropylene is generally used in TPO applications, catalyst systems which yield predominately isotactic polypropylene are preferred. In addition, polypropylene impact copolymers, as well as reactor TPOs, may be used.
- the elastomeric component comprises either ethylene/alpha-olefin elastomeric copolymers or ethylene/alpha-olefin/diene terpolymers which impart flexibility and impact strength to the polypropylene matrix.
- the elastomeric component is present in the TPO in an amount ranging from at least 10 weight percent based on the total composition with from 20 to 40 weight percent preferred.
- the alpha-olefin is selected from the group consisting of C 3 to C 20 alpha olefins with propylene, butene and octene preferred and propylene most preferred.
- the ethylene content of the copolymers ranges from 80 to 45 weight percent with 65 to 45 weight percent preferred.
- the number average molecular weight of the polymers can range from 30,000 to 500,000 with from 50,000 to 100,000 preferred.
- the alpha olefin is again selected from the group consisting of C 3 to C 20 alpha olefins with propylene, butene and octene preferred and propylene most preferred.
- the diene component is selected from the group consisting of C 4 to C 20 dienes. The preferred are non-conjugated dienes. Examples of suitable dienes include straight chain, hydrocarbon di-olefin or cylcloalkenyl-substituted alkenes having from 6 to 15 carbon atoms.
- Specific examples include (a) straight chain acyclic dienes such as 1,4-hexadiene and 1,6-octadiene; (b) branched chain acyclic dienes such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene; and the mixed isomers of dihydro-myricene and dihydro-ocinene; (c) single ring alicyclic dienes, such as 1,3 cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene; (d) multi-ring alicyclic fused and bridged ring dienes such as tetrahydroindene; methyl-tetrahydroindene; dicyclopentadiene (DCPD); bicyclo-(2.2.1)-hepta-2,5-diene; alken
- the preferred dienes are dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbomene, and 5-ethylidene-2-norbornene.
- Particularly preferred diolefins are 5-ethylidene-2-norbornene; 1,4-hexadiene, dicyclopentadiene and 5-vinyl-2-norbornene.
- the terpolymers may have an ethylene content of from 80 to 45 weight percent with 65 to 45 weight percent preferred.
- the alpha olefin content may range from 20 to 55 weight percent, with 30 to 55 weight percent preferred.
- the diene content may range from 0.5 to 10 weight percent with 0.5 to 7 weight percent preferred.
- the number average molecular weight of the terpolymers can range from 30,000 to 500,000 with from 50,000 to 100,000 preferred.
- the elastomers used in the practice of the invention can be linear, substantially linear, blocky or branched. Of these, branched elastomers are preferred as they produce the highest impact strength when compared to other elastomers of equivalent Mooney viscosity.
- the presence and degree of branching are determined from molecular weight measurements.
- Molecular weights are measured using both conventional gel permeation chromatography with a differential refractive index detector (DRI) and Low Angle Laser Light Scattering (LALLS) detector.
- DRI differential refractive index detector
- LALLS Low Angle Laser Light Scattering
- Lower moments of the molecular weight distribution, such as number average molecular weight (M n ) are obtained using DRI.
- M w weight average molecular weight
- M z Z average molecular weights
- the relative degree of branching is quantified using the branching index [BI]. This index is calculated from measured values of (i) M w , LALLS (ii) M w , DRI (iii) viscosity average molecular weight M v , DRI and (iv) inherent viscosity (IV) measured in decalin at 135 °C.
- the branching index for a linear polymer is 1.0, and for branched polymers, the extent of branching is defined relative to a linear polymer. For a medium branched polymer, the branching index ranges from 0.5 to 0.7, while for highly branched polymers BI values range from 0.1 to 0.3.
- Linear elastomers can be prepared using a conventional polymerization process including traditional Ziegler-Natta catalysts as well as metallocene catalysts. Substantially linear polymers are described in U.S.-A-5,272,336 and 5,278,272. Branched elastomers can be made in a similar fashion as disclosed in U.S.-A-5,674,613. Block copolymers can be manufactured using the technique described in U.S.-A-4,792,595 and include Vistalon® 878 and MDV 91-9 made and sold by Exxon Chemical Company.
- the high propylene copolymer compatibilizer used in this invention comprises an ethylene/propylene copolymer having a propylene content of at least 80 weight percent up to 92 weight percent.
- the propylene content may range from 83 to 91 weight percent with 85 to 90 weight percent most preferred.
- the number average molecular weight of the copolymer ranges from 40,000 to 300,000 with from 80,000 to 200,000 preferred.
- the copolymers will have a molecular weight distribution defined by a ratio, of weight to number average molecular weight of generally from 1.8 to 4.5 with from 2 to 3 preferred.
- the copolymers are random copolymers of ethylene and propylene having long sequences of propylene monomers interrupted by ethylenes.
- copolymers act as compatibilizers between the polypropylene matrix and the elastomer component resulting in better dispersion of the elastomer throughout the polypropylene matrix. This increased dispersion, in turn, results in improved impact strength as well as other physical properties.
- the propylene content of the copolymers is such that as contrasted with conventional ethylene/propylene copolymers, the copolymers exhibit a high degree of tacticity in the propylene regions, i.e., the copolymers may have isotactic or syndiotactic regions. While any copolymer may be used in the practice of this invention, those copolymers having isotactic regions are most preferred.
- the use of copolymers with isotactic regions results in TPOs with superior impact strength both at room temperature and down to at least -30 °C.
- the presence of isotactic sequences in the copolymer can be determined by examining the crystallinity of the copolymer.
- the preferred copolymers of the invention should have a crystallinity of from 2% to 65% that of isotactic homopolypropylene, preferably between 5% and 40%, as measured by the heat of fusion of annealed samples of polymer
- one means for preparing the high propylene copolymers useful in this invention is as follows: (1) ethylene and propylene are introduced into a stirred tank reactor, (2) the catalyst system is introduced via nozzles, (3) solvent is fed to the reactor, (4) the reactor contains a liquid phase composed of propylene, together with ethylene, optional diene, solvent and polymer, (5) the reactor temperature and pressure may be controlled via autorefrigeration, as well as by cooling coils, jackets, feed regulation, etc., (6) the polymerization rate is controlled by the concentration of catalysts, monomer and temperature, and (7) the ethylene content of the polymer product is determined by the ratio of ethylene to propylene in the reactor, which is controlled by manipulating the feed rates of these components into the reactor.
- a typical polymerization consists of a polymerization in the presence of a catalyst system comprising a cyclopentadienyl-containing transition metal compound (hereinafter referred to as a metallocene) and an activator.
- a metallocene cyclopentadienyl-containing transition metal compound
- an activator a cyclopentadienyl-containing transition metal compound
- metallocene catalysts which impart a high degree of isotacticity in the final product are preferred.
- Catalysts meeting this requirement include the chiral metallocene catalysts described in U.S.-A-5,198,401.
- Activator which can be used as part of the catalyst system include alumoxanes and non-coordinating anion compounds. Of these, the non-coordinating anion activators are preferred.
- the alumoxane activator is preferably used in an amount to provide a molar aluminum to metallocene ratio of from 1:1 to 20,000:1 or more.
- the non-coordinating anion activator is preferably used in an amount to provide a molar ratio of metallocene to non-coordinating anion of from 10:1 to 1:1.
- the above polymerizations are conducted in the present of the catalyst system at a temperature of from -100 °C to 300 °C for a time of from 1 second to 10 hours to produce a copolymer having a weight average molecular weight of from 40,000 to 300,000 and a molecular weight distribution of generally from 1.8 to 4.5.
- the process used to prepare the high propylene copolymer includes using a catalyst in the liquid phase, (slurry, solution, suspension or bulk phase or combination thereof), according to other embodiments, high pressure fluid phase or gas phase polymerization processes may also be used.
- the catalyst system will generally employ supported catalyst. See, for example, U.S.-A-5,057,475.
- Such catalyst systems can also include other well-known additives such as, for example, scavengers.
- the liquid phase process comprises the steps of contacting ethylene and propylene with a catalyst system in a suitable polymerization diluent and reacting the monomers in the presences of the catalyst system for a time and at a temperature sufficient to produce an ethylene/propylene copolymer of the desired molecular weight and composition.
- the compatibilizers of the invention are generally used in an amount ranging from 2 to 15 weight percent of the TPO composition with from 3 to 7 weight percent preferred.
- the TPOs of the present invention can be prepared by any conventional method currently employed in the manufacture of TPOs.
- the individual components can be separately manufactured and mechanically blended together.
- two or more of the components can be prepared in a reactor blend.
- the components are combined in a mechanical mixer, such as a BR Banbury mixer and mixed at high intensity.
- Mixing intensity is controlled until the polypropylene component melts (or fluxes) and forms a homogenous mixture.
- Mixing is continued for 2 minutes after flux of the polypropylene and the intensity is regulated such that the batch temperature does not exceed 210 °C.
- the compound is then discharged from the mixer and finished using conventional finishing techniques.
- the homopolymers are produced using traditional Ziegler-Natta catalysts and have the properties recited in Table I. TABLE I Polypropylene Characteristics Escorene® PP 1105 19062-002-001 Melt Flow Rate @ 230 °C gm/10 min.
- the elastomers used in the following examples were prepared from traditional catalyst systems.
- Vistalon® 606 and Vistalon® 878 are ethylene-propylene copolymers made and sold by Exxon Chemical Company.
- Royalene® 521 is an ethylene-propylene-diene terpolymer made and sold by Uniroyal.
- Elastomers 6-1 and 7-2 are developmental ethylene-propylene-diene terpolymers. These terpolymers are highly branched.
- the composition and physical characteristics of the elastomers are summarized in Table II. TABLE II Elastomer Characteristics Polymer Vistalon® 878 Vistalon® 606 6-1 7-2 Royalene ® 521 ML (1+4) @ 125°C MU.
- Ethylene and propylene feeds were combined into one stream and then mixed with a prechilled hexane stream that had been cooled to 0 °C. If ENB was used, it was also fed into the hexane stream upstream of the other monomers.
- a hexane solution of triisobutyl aluminum or tri(n-octyl) aluminum scavenger was added to the combined solvent and monomer stream just before it entered the reactor to further reduce the concentration of any catalyst poisons.
- the aluminum alkyl/metallocene molar ratio was typically 10 - 100.
- the polymer was characterized to give Mooney viscosity (by Mooney Viscometer, ASTM D1648), ethylene content (by FTIR, ASTM D3900), ENB content (by FTIR, ASTM D6047), melt temperature and/or glass transition temperature (by DSC, described herein), and molecular weight (by GPC, described herein). Analysis of the second reactor polymer represents the properties of the overall polymer blend.
- GPC Gel Permeation Chromatography
- DSC Differential scanning calorimetry
- composition and physical characteristics of the compatibilizers are reflected in Table III.
- the TPO compositions were formulated in a BR Banbury mixer using a batch size of 1260 grams.
- the relative proportions of the polymer components are reflected in Tables. All the polymer components were simultaneously charged into the Banbury chamber and were mixed at 85 RPM motor speed. The temperature inside the mixing chamber was allowed to rise above the melting point of the polypropylene component (165°C) at which point the polypropylene melts (fluxes) and forms a homogeneous mixture. Mixing was continued for 2 minutes after the flux point of the polypropylene and the rotor speed was adjusted so that the batch temperature of the TPO composition did not exceed 200°C. The compositions were then discharged from the Banbury and then ground into pellets.
- Standard test specimens as required by ASTM methods, were prepared by injection molding using a 75 ton Van Dorn injection molding equipment. Physical properties of the various samples were measured as described in Table V below.
- the Exxon Test Method is described in T. Yu and N. R. Dharmarajan "Preparation and Morphological Studies of Metallocene Plastomers Modified Polypropylene Blends", Soc. Plast. Eng., Proc. (ANTEC) , May, 1996.
- TPO compositions were prepared in accordance with the procedure outlined above to examine what effect different combinations of polymers have on the TPO characteristics.
- Table V Various TPO compositions were prepared using a polypropylene homopolymer having an MFR of 35.
- Compatibilizer A is used by itself as an impact modifier.
- Examples 2 and 3 show the effect this compatibilizer has in combination with a branched elastomer.
- Example 4 shows improved melt flow when compared with Example 2 having no compatibilizer.
- Examples 4 and 5 also illustrate the compositions of the invention.
- Example 4 comprises a polypropylene homopolymer with a highly branched elastomer modifier. No compatibilizer is present.
- Example 5 is the same combination but with 10 weight percent of compatibilizer substituting for the branched elastomer. Again, the addition of the compatibilizer significantly improves the melt flow of the composition while leaving the other TPO properties unaffected.
- Example 6 is a comparative example formulated with Uniroyal's Royalene® 521, a commercially available EPDM elastomer. As shown in Table V, the resulting TPO has good physical properties but reduced melt flow as compared to Examples 3 and 5.
- Examples 7 through 13 were prepared using a polypropylene homopolymer having an MFR of 70.
- a TPO was prepared using elastomer 6-1 as an impact modifier.
- Example 8 is essentially the same except that a portion of the elastomer was replaced with Compatibilizer A. As seen in Table VI, Example 7 exhibits poor impact properties. Example 8, however, exhibits improved impact.
- Examples 9 and 10 are similar to examples 7 and 8 with the exception that Elastomer 7-2 is used in lieu of Elastomer 6-1. Again, the formulation with the compatibilizer exhibited improved impact strength and melt flow when compared to the control formulation.
- Example 11 shows a control formulation using a linear/blocky ethylene propylene copolymer (V 878) as the modifier. The impact strength of this TPO compound is low.
- Example 12 shows a composition similar to Example 11, wherein 5% of the compatibilizer B is used as substitute for V 878. This composition shows marginally improved impact properties over Example 11. When compared to Example 8, containing the branched EPDM polymer 6-1, the impact improvement seen in Example 12 is inadequate.
- Example 13 is another control formulation using Uniroyal Royalene® 521. Again, the impact properties are inferior to those achieved using the compatibilizer.
- Examples 14 to 18 show the effect of ethylene content in the compatibilizer on TPO properties. As shown in Table VII, as ethylene content decreases, both Izod impact and Gardner impact strengths decrease. TABLE VII Effect of Compatibilizer Ethylene content on TPO properties 14 15 16 17 18 PP 19062-002-001 (70 MFR) wt % 70 70 70 70 70 Elastomer 6-1 30 25 25 25 25 25 Compatibilizer C - 5 - - - D - - 5 - - E - - - 5 - F - - - - 5 Irganox® 1010 0.2 0.2 0.2 0.2 0.2 0.2 Notched Izod Impact J/m 21° C 75 578 583 166 155 -30° C 48 75 91 54 54 -40° C 59 102 86 75 70 Gardner Impact @ -29° C J Total Energy 6.8 >36 >36 28 - Failure Type SB D D D/DB - Flexural Modulus @ 13 mm/min MPa
- the morphology of a series of TPO samples were examined using both LVSEM and TEM.
- LVSEM analysis thin sections of the sample were cut from injection molded specimens. The sections were obtained along the flow direction. These specimens were stained with RuO 4 prior to analysis.
- Figures 1B and 1A show the dispersion of the elastomer phase in a 70 MFR polypropylene matrix for compositions with and without the compatibilizer. From the LVSEM images, it is apparent that in the TPO compositions without the compatibilizer, the elastomer phase is uneven with particles >5 micrometers. In contrast, the TPO composition containing a compatibilizer exhibits good dispersion of the elastomer phase with a particle size of about 1 micrometer Additionally, a very fine dispersion of the elastomeric phase is noticed in the TPO composition with the compatibilizer, which is not seen in the TPO composition containing the elastomer alone.
- Figures 2B and 2A show TEM images of compositions with and without the compatibilizer.
- the interface between the polypropylene and elastomer phases is distinct, with no interpenetration of the two phases.
- the TEM image of the compatibilizer containing TPO composition shows a halo between the polypropylene matrix and the elastomer phase as well as crystalline lamellae extending from the polypropylene phase into the elastomer phase.
- the inventors believe that the interface is occupied by the compatibilizer as shown by the image and that the interpenetration leads to improved interfacial adhesion resulting in improved impact properties.
- FIGS 3A and 3B show a schematic of a section examined after fracturing the specimen. The top surface of the section contains the fracture plain and is included in the analysis.
- Figures 4A to 4D show the corresponding fracture micrographs from the TPO compositions with and without the compatibilizer.
- the fracture mode is predominantly cavitation or void formation within the rubber phase (white domains seen inside the rubber particles correspond to rubber cavitation) with some indication of craze formation in the PP matrix.
- the compound with the compatibilizer shows none of the above features near the notch KP.
- the region containing the notch has elongated rubber particles with no indication of cavitation. No crazes are formed in the PP matrix. Proceeding towards the bottom of the specimen, away from the notch surface, the failure mode is a combination of crazing and cavitation as observed in the control specimen.
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- Organic Chemistry (AREA)
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US3346396P | 1996-12-17 | 1996-12-17 | |
US33463P | 1996-12-17 | ||
PCT/US1997/023273 WO1998027154A1 (en) | 1996-12-17 | 1997-12-16 | Themoplastic olefin compositions |
Publications (2)
Publication Number | Publication Date |
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EP0946640A1 EP0946640A1 (en) | 1999-10-06 |
EP0946640B1 true EP0946640B1 (en) | 2002-02-27 |
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Application Number | Title | Priority Date | Filing Date |
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EP97952488A Expired - Lifetime EP0946640B1 (en) | 1996-12-17 | 1997-12-16 | Thermoplastic olefin compositions |
EP97951719A Withdrawn EP0946641A1 (en) | 1996-12-17 | 1997-12-16 | Thermoplastic elastomeric compositions |
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EP97951719A Withdrawn EP0946641A1 (en) | 1996-12-17 | 1997-12-16 | Thermoplastic elastomeric compositions |
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US (1) | US6268438B1 (es) |
EP (2) | EP0946640B1 (es) |
JP (2) | JP2001524139A (es) |
KR (2) | KR20000057589A (es) |
CN (2) | CN1195797C (es) |
AU (2) | AU731537B2 (es) |
BR (2) | BR9713748A (es) |
CA (2) | CA2273794A1 (es) |
DE (1) | DE69710778T2 (es) |
ES (1) | ES2173510T3 (es) |
IL (2) | IL130346A0 (es) |
MY (1) | MY114053A (es) |
TW (1) | TW479064B (es) |
WO (2) | WO1998027155A1 (es) |
Cited By (1)
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US11186708B2 (en) | 2017-06-29 | 2021-11-30 | Borealis Ag | Polypropylene composition with outstanding impact performance |
Families Citing this family (98)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6245856B1 (en) * | 1996-12-17 | 2001-06-12 | Exxon Chemical Patents, Inc. | Thermoplastic olefin compositions |
US6635715B1 (en) | 1997-08-12 | 2003-10-21 | Sudhin Datta | Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers |
US6288171B2 (en) * | 1998-07-01 | 2001-09-11 | Advanced Elastomer Systems, L.P. | Modification of thermoplastic vulcanizates using random propylene copolymers |
US7035400B1 (en) | 1999-03-01 | 2006-04-25 | Wm. Marsh Rice University | Signaling Techniques in channels with asymmetric powers and capacities |
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EP0946640A1 (en) | 1999-10-06 |
KR20000057589A (ko) | 2000-09-25 |
EP0946641A1 (en) | 1999-10-06 |
WO1998027154A1 (en) | 1998-06-25 |
JP2001524139A (ja) | 2001-11-27 |
AU731184B2 (en) | 2001-03-29 |
CA2273794A1 (en) | 1998-06-25 |
BR9713748A (pt) | 2000-03-21 |
CN1195797C (zh) | 2005-04-06 |
AU5608198A (en) | 1998-07-15 |
TW479064B (en) | 2002-03-11 |
JP2002501555A (ja) | 2002-01-15 |
US6268438B1 (en) | 2001-07-31 |
MY114053A (en) | 2002-07-31 |
AU731537B2 (en) | 2001-03-29 |
IL130104A0 (en) | 2000-06-01 |
DE69710778D1 (de) | 2002-04-04 |
DE69710778T2 (de) | 2002-08-22 |
ES2173510T3 (es) | 2002-10-16 |
KR100491237B1 (ko) | 2005-05-25 |
CN1244208A (zh) | 2000-02-09 |
CA2274531A1 (en) | 1998-06-25 |
KR20000057588A (ko) | 2000-09-25 |
CN1251603A (zh) | 2000-04-26 |
WO1998027155A1 (en) | 1998-06-25 |
IL130346A0 (en) | 2000-06-01 |
BR9714409A (pt) | 2000-04-18 |
AU5528698A (en) | 1998-07-15 |
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